Ether-plasticized compositions



Patented Feb. 12, 1952 ETHER-PLASTICIZED COMPOSITIONS George L. Doelling, St. Louis, and KennethH. Adams, Fenton, Mo., assig'uo'rs" to Mississippi Valley Research Laboratories, Inc., St. Louis, Mo., a. corporation of Missouri'- No Drawing. Application March 16, 1950 Serial No. 150,107

This invention relates to ether-plasticized com positions and more particularly to compositions plasticized with polyethylene glycol bis (nitrophenyl) ethers.

This application is a continuation-in-part of our copending application, Serial No. 764,926, filed July 30, 1947, now Patent Number 2,527,506.

Briefly, the invention comprises plasticizable organic compositions which are plasticized with compounds having the formula:

x, common-0 X in which X represents chlorine or bromine, m is an integer greater than three and less than thirty, and n is an integer from zero to three inclusive.

Among the several objects of this invention may be noted the provision of new and useful'plasticized compositions of plasticizable organic materials and polyethylene glycol bis (nitrophenyl) ethers. Other objects will be in part apparen and in part pointed out hereinafter.

19 Claims. (01. 260-33.2)

sitions of the present invention and the derivatives of said ethers, represented by the foregoing formula, include polyethylene glycol bis (nitrophenyl) ethers .and their derivatives which have oneor more methyl, ethyl, isopropyl, etc. groups substituted for hydrogen in one or both of the nitrophenyl nuclei.

, Among these ethers employed in the plasticized compositions of the present invention are nonaethylene glycol bis (paranitrophenyl) ether,

' hexaethylene glycol bis (paranitrophenyl) ether,

tetraethylene glycol bis (paranitrophenyl) ether, tridecaethylene glycol bis -(paranitrophenyl) ether, tridecaethylene glycol bis (orthonitrophenyl) ether, docosaethylene glycol bis (paranitrophenyl) ether, hexaethylene glycol bis (2- chloro 4 nitrophenyl) ether, tridecaethylene glycol bis (chloronitrotolyl) ether, nonaethylene glycol bis (4-bromo-2-nitrophenyl) ether, nonaethylene. glycol bis (4-chloro-2-nitrophenyl) ether, hexaethylene glycol bis (dichloronitrophenyl) ether, nonaethylene glycol bis (di chloro nitrophenyl) ether, tridecaethylene glycol bis (2-chloro-4-nitrophenyl) ether, docosaethylene glycol 'bis l-ohloro-Z-nitrophenyl) ether and tridecaethylene glycol bis (dichloronitrophenyl) The invention accordingly comprises the ingredients and combinations of ingredientatheproportions thereof, and features of composition 1TIO2 in which X represents chlorine or bromine, m is an integer greater than three and less than thirty, and n is an integer from zero to three inclusive. The (CH2CH2)mO-group may be substituted in any position in the nitrophenyl nucleus not otherwise occupied. The chlorine or bromine may be similarly substituted.

The ether components of the plasticize compoether.

These ethers may, in most instances, be convehiently made by the reaction of a halonitrobenzene and a polyalkylene glycol. In general the halonitrobenzene is mixed with the proper polyalkylene glycol, the mixture is heated to a. temperaturenot over 100 0;, a current of oxygen or an oxygen containing gas is passed through or over the solution and an alkaline material is added, preferably in a number of portions as the reaction progresses, in order to avoid havin a high concentration of alkali in the solution at any time during the'reaction. To make these polyethylene glycol bis (nitrophenyl) ethers the molar ratioof halonitrobenzene to polyalkylene glycol is preferably maintained at a ratio of at least2:1.

,For best results the concentration of alkali in the reaction mixture during the reaction should be kept less than 1.0 normal, and we prefer to keep it 0.5 normal or less; that is, l milliliter of the reaction mixture when titrated in an aqueous acetone solution to phenolphthalein indicator, should preferably take not over 1 milliliter of 0.5 normal HCl solution to neutralize it.

The oxygen or oxygen containing gas is preferably passedinto the reaction mixture throughout the reaction in order to keep an appreciable amount of oxygen in solution at all times. Keep- 3 ing oxygen or an oxygen containing gas under pressure over the solution also aids in keeping an appreciable amount of oxygen in solution in the reaction mixture. This prevents reduction of the nitro group to azoxy or other reduction products.

The reaction mixture should preferably be stirred during the entire run and we prefer to run the reaction at the lowest temperature at which a reasonably rapid rate of'reaction will occur in any given case. This rate of reaction can be determined from titration of samples taken out at intervals. As can be seen from the subsequent examples, we prefer a temperature from 35 C. to 85 C., though higher temperatures can be used. At too high a temperature, over about 100 C., the tendency to reduction and side reactions is very great in most cases.

The plasticized compositions of the present invention include plasticizablerorganic materials plasticized with the above mentioned polyethylene glycol bis (nitrophenyl) ethers. Such plasticizable materials are exemplified by phenolformaldehyde resins, vinyl resins (e. g. vinyl chloride-vinyl acetate copolymers), and cellulose esters such as cellulose acetates (including cellulose acetate-butyrate) and cellulose nitrate.

The following examples illustrate the invention:

Example 1 Nonaethylene glycol bis ether, having the formula:

(paranitrophenyl) womonm-o was made from paranitrochlorobenzene and nonaethylene glycol, as follows:

The nitrochlorobenzene and the nonaethylene glycol were charged into a 500 milliliter, S-neck, round-bottomed flask equipped with a reflux condenser, a mechanical stirrer and an inlet tube for oxygen. The materials were heated to about 55 C. and then a slow stream of oxygen gas was bubbled-continuously through the batch during the entire run, to prevent reduction of the nitro group. Then with oxygen going through and the stirrer running, 6 grams of potassium hydroxide were added. At a temperature of 55 to 60 C. the remainder of the alkali was added in 6 gram portions over a period of about 5 hours. The addition of the alkali was at about the same rate as it was used up in the reaction,

as determined by removin samples at intervals and titrating the free alkali present in the batch. A 1 milliliter sample of the batch titrated from zero to about 5 milliliters of .1 N HCl to phenolphthalein at various times during the run. Total time of reaction was about 6% hours.

The batch was wroked up by diluting with water and then extractingwith a mixture of benzene and isopropyl ether. The combined extracts were washed several times with water. After removal of solvent the excess nitrochlorobenzene was distilled off under a vacuum of about 2 millimeters. The product was a reddishamber, rather viscous oil. Its molecular weight by the camphor method was 647 against 642, the theoretical value for this compound. It is soluble in alcohol and acetone but is soluble in water only to the extent of about 0.13% by weight at 25 C.

This product is useful as a cellulose nitrate plasticizer. Ten grams of cellulose nitrate and 10 grams of the nonaethylene glycol bis (paranitrophenyl) ether were dissolved in 100 milliliters of a mixture of equal parts of absolute ethyl alcohol and n-butyl acetate. This solution was then floated onto a glass slide and the solvent evaporated off. A clear film resulted which remained clear. This ether is also compatible with cellulose acetate up to 25% or more of the weight of the cellulose acetate.

Example 2 Hexaethylene glycol bis ether, having the formula:

NO: $02 i (paranitrophenyl) dish-amber oil which had approximately the correct molecular weight for this compound. It was found to be soluble in alcohol, benzene and other common solvents, but in water only to the extent of about .08% by weight at 25 C.

This ether is useful as a plasticizer for cellulose nitrate. A solution was made up of mililiters of a mixture of equal amounts of absolute ethyl alcohol and n-butyl acetate, 10 grams of cellulose nitrate and 10 grams of the hexaethylene glycol bis (paranitrophenyl) ether. Some of this solution was floated onto a glass slide and the solvent allowed to evaporate. The resulting film was clear and remained clear after exposure to the air, showing that this ether is compatible with cellulose nitrate over a wide range of proportions. This ether was also found to be compatible with cellulose acetate in the proportion of about 20% of the weight of the cellulose acetate.

Example 3 Tetraethylene glycol bis (paranitrophenyl) ether, having the formula:

N02 TT Z The bis (paranitrophenyl) ether of polyethylene glycol corresponding approximately to the formula:

NO; NO:

was made from paranitrochlorobenzene and a polyethylene glycol having a molecular weight of approximately 600. From 180 grams .of such polyethylene glycol a yield of 231 grams of this ether was secured. The product had approximately the correct molecular weight and was soluble in water to the extent of about 32% by weight at 25 C. It was a rather viscous reddish,- brown oil.

The bis (orthonitrophenyl) ether of the same polyethylene glycol was also made and had properties very similar to the para compound.

This bis (paranitrophenyl) ether of polyethylene glycol having a molecular weight of approximately 600 was tested for compatibility with a phenol formaldehyde resin made from tertiary-butyl phenol and formaldehyde. A film made in the manner described above containing 25% of this ether on the weight of 'the phenol formaldehyde gave a clear film after baking it at 140 to 145 C. for 40 minutes.

Example 5 The bis (paranitrophenyl) ether ofpolyethylene glycol corresponding approximately to the formula:

was made from parachloronitrobenzene, a, poly-' ethylene glycol having a molecular weight of approximately 1000 and potassium hydroxide. The reaction was run at 70 to 72 C. for about 6 hours. The product recovered in the usual manrier from this reaction-mixture, was a rather viscous amber oil, soluble in alcohol and acetone but soluble in water only to, the extent of about" Example 6 Hexaethylene glycol bis (2-chloro-4-nitrophenyl) ether havingthe formula: r

. memories-o was made from hexaethylene glycol and 3,4-dichloronitrobenzene, in a manner similarto Example l. as follows! Weight Mus grams 3,4-Dich1oronitrobenzene 152 79 Hexaethylene Glycol 90 .30

Potassium hydroxide (90% flakes) 41 I .66

The product weighed 151 grams and was a rather viscous, reddish oil. It was soluble in alcohol, benzene and ketones but soluble in water only to the extent of about 008% by weight at nitrate.

' Ten grams of Resinox (a phenol-formaldehyde condensation polymer) molding resin and .5 grams of the hexaethylene glycol bis (Z-chloro- 4-nitrophenyl) ether were dissolved in 50 milliliters of a mixture of equal volumes of ethyl,.al-.. cohol and methyl ethyl ketone. A small amount.

of this solution after filtering was floated onto a glass slide and the solvent evaporated. This left a clear film and after heating the film at about C. for 20 minutes the film was still clear. A.

similar test was made with 25% of the weight of resin of this same ether, giving about the same result. The plasticized resin is less-brittle after curing than when no plasticizer is used.

Example 7 was made from 2,6-dichloro-3-nitrotoluene and a polyethylene glycol having a molecular weight of approximately 600 in a manner similar to Ex-' ample 6.

, The product was a viscous reddish oil soluble in alcohol, acetone and benzene but practically insoluble in water.

This ether was tested for compatibility with a vinyl chloride vinyl acetate copolymer resin H similar to that employed in Example 5. It gave a clear film with 25% of this ether on of the vinyl resin.

Some oi'this solution was floated the weight- 1"- Emample 8 was made from 2,5-dibromonitrobenzene and nonaethylene glycol in a manner similar to'E'xample 6.

The product was a reddish oil which had approximately the correct molecular weight for this compound. It was soluble in alcohols and ketones but practically insoluble in water.

This ether was tested for compatibility with cellulose acetate-butyrate. A solution was made of grams of cellulose acetate-butyrate (16% butyryl) in a mixture of acetone and methyl Cellosolve, then 2.5 grams of this ether was dissolved in this solution. A film cast from this solution in the usual manner was clear showing that this ether is compatible at least up to 25% of the weight of the cellulose acetate-butyrate.

Example 9 Nonaethylene glycol bis (4-chloro-2-nitrophenyl) ether, having the formula:

V 7 N02 NO;

Example 10 Hexaethylene glycol bis (dichloronitrophenyl) ether, having the formula:

IIIO: I IITO: 012 goomcnm-ofich was made from 2,4,5-trichloronitrobenzene and hexaethylene glycol in a manner similar to Example 6. In this case though the reaction was carried out at 46 C. to 48 C. and the time of reaction was only 4 hours. The product had about the correct molecular weight for this compound and consisted of a rather viscous dark-red oil. This compound was soluble in water only to the extent of .008% by weight at 25 C. but it was soluble in alcohols and ketones.

This ether is useful as a cellulose nitrate plasticizer. Tests have shown that it is compatible in a ratio at least up to 100% of the weight of the cellulose nitrate.

Example 11 the formula:

approximately to '01. oomoHm-o 01,

was made from nonaethylene glycol and 2,4,5- trichloronitrobenzene as follows:

Weight Mols grams 2,4,5-Triohloronitrobenzen 136 0. 60 Nonaethylene Glycol"..- 25 Sodium hydroxide 22 55 This ether was prepared in a manner similar to Example 1. The temperature of reaction was 49 to 51 C. and time of reaction was about, 5 hours. The product was isolated in the usual manner, except that in the vacuum distillation of the excess trichloronitrobenzene a current of CO2 was run through to aid in the removal of this product. This ether was an amber oil weighing 193 grams or about 99% of theory yield. It is soluble in most organic solvents except petroleum hydrocarbons.

This ether was tested for compatibility with vinyl chloride-vinyl acetate copolymer resin similar to that described in Example 5 (which may be purchased under the trade-mark VYl-IF). Ten grams of this vinyl resin was dissolved in a mixture of methyl ethyl ketone and ethylene glycol ethyl ether, then 2.5 grams of this ether were dissolved in this solution. A film cast from this solution in the manner described above was clear and flexible.

Example 1 The bis (2-chloro-4-nitrophenyl) ether of polyethylene glycol corresponding approximately to the formula:

- through the reaction mixture during the reaction.

The product recoveredin the usual manner was an amber colored oil weighing 245 grams (from grams of the polyethylene glycol used). This ether is soluble in a1cohols',.acetone and other solvents but is soluble in water'only to the extent of .05% by weight at 25 C.

This ether was also tested for compatibility with both the Example 5 and Example 11 vinyl chloride-vinyl acetate copolymer resins, in the manner previously described, and it was found to be compatible with each of these resins at least tothe extent ;of 25% ofthe weight of the resin, giving clear, flexible films in each case.

This ether was also tested for compatibility with phenol-formaldehyde resin. Five grams of phenol-formaldehyde resin (which is exemplified in the trade-marked composition Durite S31l2) were dissolved in five grams of a mixture of acetone and ethyl alcohol, then two grams 1 her similar to previous examples.

:or this ether were dissolved in this solution." A

film was cast from this solution on a metal slide in the manner described above. After drying off the solvents, the film was baked at 135 to 140 C..for 15 minutes. The resulting film'was clear.

'It-was hard and apparently less brittle than when no plasticizer was added. This ether is compatible with phenol-formaldehyde resin at least up to 40% of the weight of the phenol-formaldehyde resin.

Example 13 The bis (4-chloro-2-nitrophenyl) ether of polyethylene glycol corresponding approximately ,to

the formula:

It was found to be compatible at least up to 25% of the weight of the vinyl resin, and gave a clear flexible film.

Example 14 The bis (dichloronitrophenyl) ether of polyethylene glycol corresponding approximately to the formula:

was made from 2,4,5-trichloronitrobenzene, a polyethylene glycol having a molecular weight of approximately 600, and sodium hydroxide in a manner similar to previous examples. Oxygen was bubbled through the reaction-mixture during the reaction. The temperature of reaction was 50 C. to 52 C. and the time of reaction was about 5 hours.

This ether was tested for compatibility with cellulose acetate-butyrate in the manner described in Example 8. It was found to be compatible at least up to 25% of the weight ofthe cellulose acetate-butyrate, giving a film that was clear and flexible.

Polyethylene glycol ethers containing fewer than four ethylene groups are unsuitable for use.

as plasticizers for plastic and polymeric materials. They are accordingly not within the purview of, our invention.

In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

As many changes. could be made in the-above methods and products without departing from the scope of the invention, it is intendedthat all matter contained in the above description shallbe interpreted as illustrative and not in a limiting sense.

We claim;

1. A plasticized. composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters, phenolformaldehyde resins and vinyl resins, and as a plasticizer therefor, a compound having the formula:

x. oomoHem-o in which X represents, a halogen selected from the group consisting of chlorine and bromine, 'm is an integer greater than three and less than thirty, 11. is an integer includingzero and not greater than three, and in which any hydrogen atom in the phenyl nuclei may be substituted by a lower alkyl group.

2. A plasticized composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters, phenol-formaldehyde resins and vinyl resins, and as a plasticizer therefor, a compound having the formula:

NO: IITO:

in which 711. is an integer greater less than thirty. I

3. A plasticiz'ed composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters, phenol-formaldehyde resins and vinyl resins, and as a plasticizer therefor, a compound having the formula:

' NO; NO:

than three and.

' or ocmcnero o1 in which m is an integer greater than three and less than thirty.

4. A plasticized composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters phenol-formaldehyde resins and vinyl resins, and as a plasticizer therefor, a compound having'the formula:

in which m is an integer greater than three and less than thirty.

5. A plasticized composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters, phenol-formaldehyde resins and vinyl resins, and as a plasticizer therefor, a compound having the formula:

in which m is an integer greater than three and less than thirty.

11 1 6. A plasticized composition comprising a plasticizable organic substance selected: from the group consisting of cellulose esters, phenol-formaldehyde resins and vinyl resins, and as a plasticizer therefor, a compound having the formula:

ITTO: ITIOZ Cl (OCHzCHz)mO Cl C a CH;

in which 121. is an integer greater than three and less than thirty.

'7. A plasticized composition comprising a cellulose ester and as a plasticizer therefor, acompound having the formula:

NO; I I

in which X represents a halogen selected from the group consisting of chlorine and bromine. m

is an integer greater than three and less than thirty, n is an integer including zero and not greater than three, and in which any hydrogen atom in the phenyl nuclei may be substituted by a lower alkyl group.

8. A plasticized composition comprising a vinyl resin and as a plasticizer therefor, a compound having the formula:

I QLJ in which X represents a halogen selected from the group consisting of chlorine and bromine, m is an integer greater than three and less than thirty, n is an integer including zero and not greater than three, and in which any hydrogen atom in the pheny1 nuclei may be substituted by a lower alkyl group.

9.,A plasticizedcomposition comprising a phe- A hol-formaldehyd resin and as a' plasticizer therefor, acompound having the formula:

in which X "represents a halogenselected from the group consisting of chlorine and bromine, m is an integer greater than three and less than thirty, 12 is an integer including zero and not greater than three, and in-which any hydrogen atom in the phenyl nuclei may be substituted by a lower alkyl group. a a

10. A plasticized composition comprising cellulose acetate and as a plasticizer therefor, a compound having the formula:

' 1 10, no; xwgoomormm-ogxn in which X represents a halogen selected from the group consisting of chlorine and bromine, m is an integer greater than three and less than -pla'stici z'able organic substance selected from the thirty, n' is aninteger including zero and not greater than three, and in which any hydrogen atom in the phenyl nuclei may be substituted by a lower alkyl group.

11. A plasticizedcomposition comprising a cellulose acetate-butyrate and as a plasticizer therefor, a compound having the formula:

in which X represents a halogen selected from the group consisting of chlorine and bromine, m is an integer greater than three and less than thirty, 11. is an integer including zero and not greater than three, and in which any hydrogen atom in the phenyl nuclei may be substituted by a lower alkyl group.

12. A plasticized composition comprising cellulose nitrate and as a plasticizer therefor, a compound having the formula:

NOz N02 in which X represents a halogen selected from the group consisting of chlorine and bromine, m is an integer greater than three and less than thirty; 11. is an integerincluding zero and not 'greater than three, and in which any hydrogen atom in the phenyl nuclei may be substituted by a lower alkyl group.

- 141 A plasticized composition comprising a group consisting of cellulose esters, phenol-formaldehyd'e resins and vinyl resins, and as a plasticizer'therefor, a compound selected from the group consisting of nonaethylene glycol bis (paranitrophenyl) ether, hexaethylene glycol bis Y (p'aran'itrophenyl) ether, tetraethylene glycol bis (paranitrophenyl) ether, tridecaethylene glycol bis"'(paranitrophenyl) ether, tridecaethylene glycol 'bis (orthonitrophenyl) ether, docosaethylene glycol bis (paranitrophenyl) ether, hexaethylene glycol bis' '(2-chloro-4-nitropheny1) ether, tridecaethylene glycol bis (chloronitrotolyl) ether, n'on'aethylene glycol bis (4-bromo-2-nitrophenyl) ether; nonaethylene glycol bis (4-chloro-2 nitro phenyl) ether, hexaethylene glycol bis (dichloro- 'nitrophenyl) ether, nonaethylene glycol bis (dichloronitrophenyl) ether, tridecaethylene glycol 'bis= (2'-chloro-4-nitrophenyl) ether, docosaethyl- 1 1 ,2-nitrophenyl) ether and tridecaethylene glycol bis (dichloronitrophenyl) ether.

15. A plasticized composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters, phenol-formaldehyde resins, and vinyl resins, and as a plasticizer therefor, hexaethylene glycol bis (paranitrophenyl) ether.

16. A plasticized composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters, phenol-formaldehyde resins, and vinyl resins, and as a plasticizer therefor, hexaethylene glycol bis (2- chloro-4-nitrophenyl) ether.

1'7. A plasticized composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters, phenol-formaldehyde resins, and vinyl resins, and as a plasticizer therefor, nonaethylene glycol bis (4- chloro-2-nitrophenyl) ether.

18. A plasticized composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters, phenol-formaldehyde resins, and vinyl resins, and as a plasticizer therefor, hexaethylene glycol bis (dichloronitrophenyl) ether.

19. A plasticized composition comprising a plasticizable organic substance selected from the group consisting of cellulose esters, phenol-formaldehyde resins, and vinyl resins, and as a plasticizer therefor, tridecaethylene glycol bis (2- chloro-4-nitrophenyl) ether.

Name Date Doelling Oct. 25, 1949 Number 

1. A PLASTICIZED COMPOSITION COMPRISING A PLASTICIZABLE ORGANIC SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF CELLULOSE ESTERS, PHENOLFORMALDEHYDE RESIN AND VINYL RESIN, AND AS A PLASTICIZER THEREFOR, A COMPOUND HAVING THE FORMULA: 